US11891530B2 - Writing gel ink - Google Patents
Writing gel ink Download PDFInfo
- Publication number
- US11891530B2 US11891530B2 US16/956,038 US201816956038A US11891530B2 US 11891530 B2 US11891530 B2 US 11891530B2 US 201816956038 A US201816956038 A US 201816956038A US 11891530 B2 US11891530 B2 US 11891530B2
- Authority
- US
- United States
- Prior art keywords
- aqueous gel
- ink according
- writing ink
- ink
- acid amide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active, expires
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- 150000004665 fatty acids Chemical class 0.000 claims abstract description 47
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 46
- 239000000194 fatty acid Substances 0.000 claims abstract description 46
- 229930195729 fatty acid Natural products 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 239000002904 solvent Substances 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003349 gelling agent Substances 0.000 claims abstract description 30
- 239000003086 colorant Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
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- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229960005323 phenoxyethanol Drugs 0.000 claims description 13
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 10
- KYMPOPAPQCIHEG-UHFFFAOYSA-N n-[2-(decanoylamino)ethyl]decanamide Chemical compound CCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCC KYMPOPAPQCIHEG-UHFFFAOYSA-N 0.000 claims description 8
- YLWQQYRYYZPZLJ-UHFFFAOYSA-N 12-hydroxy-n-[2-(12-hydroxyoctadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCC(O)CCCCCC YLWQQYRYYZPZLJ-UHFFFAOYSA-N 0.000 claims description 7
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- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920006276 ketonic resin Polymers 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- WGOROJDSDNILMB-UHFFFAOYSA-N octatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WGOROJDSDNILMB-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- WOQDVIVTFCTQCE-UHFFFAOYSA-N pentacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WOQDVIVTFCTQCE-UHFFFAOYSA-N 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000992 solvent dye Substances 0.000 description 1
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
- 239000010981 turquoise Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
- C09D11/18—Writing inks specially adapted for ball-point writing instruments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
Definitions
- the present disclosure concerns the writing ink area, in particular ink for pen.
- ball pen inks are Newtonian high viscosity solvent based ink. Due to the use of heavy glycols solvents, ball pen inks are very stable during storage since the ink doesn't dry. Therefore the ink can be used in pens without point protection. Ball pen viscosity was defined at ⁇ 15 000 mPa ⁇ s at 20° C. to avoid static leakage (static leakage corresponds to the ink drop formation on the point when the pen is stored point down, especially in hot and humid condition).
- formulator can decrease the viscosity. However in this case, rest viscosity becomes too low and static leakage dramatically increases.
- Ball pen inks being Newtonian, rest viscosity is the same as shear viscosity. The rest viscosity remaining relatively low (15 000 mPa ⁇ s at 20° C.), this prohibits the addition of pigments or other particles (due to low rest viscosity, these particles would settle in pen points and clog them).
- Gel inks have a pseudoplastic rheological profile.
- gel inks are water based. They are a perfect compromise between low static leakage, smoothness and particles stabilization. However they suffer from several drawbacks:
- Water is a light and volatile solvent. When stored without point protection (cap or hotmelt), ink in the point can dry then clog the point; cap off time of gel inks is much lower as cap off time of solvent based ball pens.
- Color is weaker than in ball point pen inks due to the inclusion of water droplets inside the ink.
- Solvent gel inks have also been described in the prior art.
- JP3078172 and JPH07-196972 describe the use of fatty acid amide wax in an oily ink composition as a thixotropic agent for imparting thixotropy to the ink such as the compounds Talen 600 from KYOEISHA CHEMICAL and DISPARLON 6500 from Kusumoto Chemicals.
- the present disclosure concerns a non-aqueous gel writing ink comprising a solvent, a coloring agent and a gelling agent, wherein the gelling agent is a mixture of silica particles and of a fatty acid amide wax, advantageously of hydrophilic silica particles and of a fatty acid amide wax.
- writing ink is intended to mean any ink which is intended to be used in a writing instrument, in particular in a pen such as a ball-pen.
- a writing ink should not be confused with a printing ink which is used in printing machines and which does not have the same technical constraints and thus the same specifications.
- a writing ink must not contain solid particles of which the size is greater than the channels of the writing instrument, in order to avoid blocking them, which would inevitably lead to writing being irreversibly stopped.
- it must allow an ink flow rate suitable for the writing instrument used, in particular a flow rate of between 10 and 300 mg/200 m of writing, advantageously between 30 and 60 mg/150 m of writing, more advantageously of 50 mg/150 m.
- the ink according to the present disclosure will be suitable for the writing instrument for which it is intended, in particular for a pen such as a ball-pen.
- a writing ink must not be too fluid, so as to avoid leaks during writing. However, it must be sufficiently fluid to facilitate the flow of the writing action.
- the writing ink being a “gel ink” (which corresponds therefore to a thixotropic ink)
- the viscosity measured at rest at a shear rate of 0.01 s ⁇ 1 ) at 20° C. is different and in particular higher than the viscosity measured with a shear rate of 100 s ⁇ 1 at 20° C. using the same rheometer such as a cone-and-plate rheometer for example Malvern KINEXUS with a cone of 40 mm and an angle of 4°.
- the viscosity of the gel ink according to the present disclosure measured at 20° C. with a cone-and-plate rheometer for example Malvern KINEXUS with a cone of 40 mm and an angle of 4° is of between 20 000 and 100 000 mPa ⁇ s, advantageously between 40 000 and 90 000 mPa ⁇ s, more advantageously between 50 000 and 80 000 mPa ⁇ s, with a shear rate of 0.01 s ⁇ 1 and advantageously between 1500 and 15 000 mPa ⁇ s, more advantageously between 1800 and 3 000 mPa ⁇ s, still more advantageously of 2000 mPa ⁇ s with a shear rate of 100 s ⁇ 1 .
- such a viscosity is stable during storage for at least three months at 40° C. and 80% relative humidity, in particular the viscosity will not have a more than 50% decrease.
- the return to viscosity at rest after shear is very quick, advantageously at most a few minutes, in order to avoid the static leakage in the minutes after writing.
- the ink according to the present disclosure is a “non-aqueous ink”.
- non-aqueous ink is intended to mean in the context of the present disclosure a water-free ink, i.e. any ink which does not contain any aqueous solvent and advantageously which does not contain any water, even in a small proportion. This is because the gelling agent contained therein makes the use of aqueous solvent needless in order to obtain a gel.
- the ink according to the present disclosure contains a solvent (which is not an aqueous solvent), in particular chosen in the group consisting of glycol ether, alcohol, and mixture thereof.
- the alcohol is a high boiling point alcohol, advantageously chosen in the group consisting of benzyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, glycerin and mixture thereof, more advantageously the alcohol is benzyl alcohol.
- glycol ether is chosen in the group consisting of diethylene glycol monoethyl ether, diethylene-glycol-mono butyl ether, dipropyleneglycol monobutyl ether, tripropylene glycol monomethyl ether, phenoxyethanol, phenoxypropanol and mixture thereof, advantageously chosen in the group consisting of phenoxyethanol, phenoxypropanol and mixture thereof.
- the solvent is phenoxyethanol.
- the solvent content of the ink according to the present disclosure is between 35 and 80% by weight, relative to the total weight of the ink, more advantageously between 45 and 75% by weight, relative to the total weight of the ink, still more advantageously between 50 and 70% by weight, relative to the total weight of the ink.
- the ink according to the present disclosure also contains a coloring agent in order to impart color to the ink according to the present disclosure.
- the coloring agent can be a pigment or a dye or a mixture thereof, in particular conventional dyes or pigments employed in non-aqueous ball point pens.
- the ink is a dye-based ink. It thus comprises at least one dye. It may also comprise several thereof.
- the dyes usable in the ink according to the disclosure may be any dyes known by the one skilled in the art, such as black, blue, red, green, violet, pink, turquoise, etc. dyes.
- the dyes usable in the ink according to the present disclosure are alcohol-soluble dyes, oil-soluble dyes, direct dyes, acid dyes, basic dyes, metallized dyes and various salt-forming type dyes, more particularly the dyes are chosen in the group consisting of azoic dyes, triarylmethane dyes, phtalocyanine derivatives dyes, xanthene dyes and mixture thereof.
- Azoic dyes contain an azoic skeleton having the formula below:
- Triarylmethane dyes contain a tryarylmethane skeleton having the formula below:
- Phtalocyanine derivatives dyes contain a phtalocyanine skeleton having the formula below:
- Xanthene dyes contain a xanthene skeleton having the formula below:
- Examples of a solvent dye usable in the ink according to the present disclosure are as follow: VARIFAST Black 3806 (C.I. Solvent Black 29), 3807 (trimethylbenzylammonium salt of C.I. Solvent Black 29), Spirit Black SB (C.I. Solvent Black 5), SPIRON Black GMH (C.I. Solvent Black 43), Solvent Black 46, VARIFAST Red 1308 (salt forming form of C.I. Basic Red 1 dye and C.I. Acid Yellow 23 dye), Solvent Red 49, VARIFAST Yellow AUM (salt forming form of C.I. Basic Yellow 2 dye and C.I. Acid Yellow 42 dye), SPIRON Yellow C2 GH (organic acid salt of C.I.
- Basic Yellow 2 SPIRON Violet CRH (C.I. Solvent Violet 8-1), VARIFAST Violet 1701 (salt forming form of C.I. Basic Violet 1 and C.I. Acid Yellow 42 dye), SPIRON Red CGH (organic acid salt of C.I. Basic Red 1), SPIRON Pink BH (C.I. Solvent Red 82), Nigrosine Base EX (C.I. Solvent Black 7), Oil Blue 613 (C.I. Solvent Blue 5), Neozapon Blue 808 (C.I. Solvent Blue 70),
- the coloring agent is a pigment known by the one skilled in the art.
- the pigment include organic, inorganic and processed pigments.
- the pigment may for example be an inorganic pigment such as a carbon black, ultramarine and titanium dioxide pigment, an organic pigment such as an azo-based pigment, phthalocyanine-based pigment, indigo pigment, thioindigo pigment, thren pigment, quinacridone-based pigment, anthraquinone-based pigment, thron-based pigment, diketopyrrolopyrrole-based pigment, dioxazine-based pigment, perylene-based pigment, perinone-based pigment and isoindolinone-based pigment, a metal pigment such as an aluminum powder or aluminum powder whose surface is treated with a colored resin, a metal gloss pigment obtained by forming a metal vapor deposition film such as that of aluminum on a transparent or colored transparent film, a metal pigment having a thickness of 0.01 to 0.1 ⁇ m obtained by peeling a metal vapor de
- the ink according to the present disclosure also comprises a gelling agent, wherein the gelling agent is a mixture of silica particles and of a fatty acid amide wax.
- silica particles are hydrophilic silica particles, in particular hydrophilic fumed silica particles, such as the product sold by Evonik under the trade name AEROSIL® 200.
- the fatty acid amide wax is a fatty acid polyamide wax, advantageously a fatty acid diamide wax, in particular chosen in the group consisting of Methylenebis stearic acid amide, N,N′-Ethylenebis(capronamide) of the following formula CH 3 (CH 2 ) 4 CONH(CH 2 ) 2 NHCO(CH 2 ) 4 CH 3 , ethylenebis capric acid amide (or N,N′-Ethylenebis(caprinamide)) of the following formula CH 3 (CH 2 ) 8 CONH(CH 2 ) 2 NHCO(CH 2 ) 8 CH 3 , Ethylenebis lauric acid amide, ethylenebis stearic acid amide, Ethylenebis hydroxystearic acid amide, ethylenebis behenic acid amide, Hexa methylenebis stearic acid amide, hexa methylenebis behenic acid amide, N,N′-distearyl adipic acid amide
- the fatty acid part of the fatty acid amide wax is chosen in the group consisting of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, hydroxystearic acid, arachidic acid behenic acid and mixture thereof.
- the fatty acid amide wax is chosen in the group consisting of N,N′-Ethylenebis(capronamide) of the following formula CH 3 (CH 2 ) 4 CONH(CH 2 ) 2 NHCO(CH 2 ) 4 CH 3 , ethylenebis capric acid amide (or N,N′-Ethylenebis(caprinamide)) of the following formula CH 3 (CH 2 ) 8 CONH(CH 2 ) 2 NHCO(CH 2 ) 8 CH 3 , N,N′-ethylenebis 12-hydroxystearic acid amide of the following formula CH 3 (CH 2 ) 5 CHOH(CH 2 ) 10 CONH(CH 2 ) 2 NHCO(CH 2 ) 10 CHOH(CH 2 ) 5 CH 3 , octadecanamide of the following formula
- the fatty acid amide wax is chosen in the group consisting of octadecanamide of the following formula
- N,N′-Ethylene-bis-12-hydroxystearamide of the following formula CH 3 (CH 2 ) 5 CHOH(CH 2 ) 10 CONH(CH 2 ) 2 NHCO(CH 2 ) 10 CHOH(CH 2 ) 5 CH 3 , N,N′-Ethylenebis(caprinamide) of the following formula CH 3 (CH 2 ) 8 CONH(CH 2 ) 2 NHCO(CH 2 ) 8 CH 3 and mixture thereof.
- the fatty acid amide wax comprises octadecanamide of the following formula
- the fatty acid amide wax is a mixture of the three following fatty acid amide waxes:
- N,N′-Ethylene-bis-12-hydroxystearamide of the following formula CH 3 (CH 2 ) 5 CHOH(CH 2 ) 10 CONH(CH 2 ) 2 NHCO(CH 2 ) 10 CHOH(CH 2 ) 5 CH 3 and
- the fatty acid amide wax is a mixture of three fatty acid amide waxes obtained by the reaction between ethylene diamine, decanoic acid and 12-hydroxystearic acid.
- the fatty acid amide wax has a melting point in the range 120° C.-130° C.
- the fatty acid amide wax according to the present disclosure is available on the market under the trade name Thixatrol® MAX from Elementis, CRAYVALLAC SUPER® from Arkema, Disparlon® 6500 from Kusumoto Chemicals and LUVOTIX® SAB from Lehmann & Voss & Co.
- the fatty acid amide wax octadecanamide alone or in admixture with N,N′-Ethylene-bis-12-hydroxystearamide and N,N′-Ethylenebis(caprinamide) is particularly useful for providing a strong gelling network whatever the type of dyes used in the ink composition such as azoic dyes, triarylmethane dyes, phtalocyanine derivatives dyes, xanthene dyes and mixture thereof.
- the fatty acid amide wax creates a network with the solvent by creating hydrogen bonds without the need of water.
- the ink is a dye-based ink, this network is strengthened by hydrogen interactions with dyes.
- the network obtained with the solvent is strong enough to obtain a gelled ink, whatever the type of coloring agent and in particular the type of dye used.
- the gelling agent content of the ink according to the present disclosure is in the range 0.1-1.2%, more advantageously in the range 0.15-0.60%, by weight, relative to the total weight of the ink.
- the fatty acid amid wax content of the ink according to the present disclosure is in the range 0.1-0.6% by weight, relative to the total weight of the ink, more advantageously in the range 0.3-0.6%.
- the silica particles content of the ink according to the present disclosure is in the range 0.05-0.8% by weight, relative to the total weight of the ink, more advantageously in the range 0.1-0.5%.
- the ink according to the present disclosure may also comprise an additive.
- This additive is generally a conventional additive of writing inks and is in particular chosen in the group consisting of clear drain agents, viscosity imparting agent, lubricant, dispersing agent and mixture thereof.
- the ink according to the disclosure may contain (by weight relative to the total weight of the ink) between 0 and 20% of the additive, advantageously between 5 and 19%, more advantageously between 10 and 17%.
- the viscosity imparting agent can be a resin which may be natural or synthetic.
- the resin can be a vinyl resin (such as a vinyl chloride copolymer, polyvinyl butyrale, polyvinylpyrrolidone, a polyvinyl acetate, a vinyl-pyrrolidone and vinyl acetate copolymer, a polyvinyl alcohol resin or a mixture thereof), an acrylic resin, a styrene-acrylic resin, a styrene-maleic acid copolymer resin, a rosin-maleic acid copolymer resin, a phenol resin, a cellulosic resin, a ketone resin, a ketone-formaldehyde resin (such as an acetophenone-formaldehyde modified resin), an amid resin, an alkyd resin, a rosin modified resin, a rosin modified phenol resin, a xylene resin, a polyacetal resin, a
- the clear drain agents can be for example sorbitan sesquioleate in particular sold under the trade name Lonzest® SOC.
- the ink according to the disclosure may contain (by weight relative to the total weight of the ink) between 0 and 5% of the clear drain agent, advantageously between 0.5 and 2%, more advantageously between 1 and 1.5%.
- the dispersing agent is particularly useful when the coloring agent is a pigment and can be Tego®Dispers 670, Tego® Dispers 671, Tego®Dispers 672, Tego®Dispers 685, Tego®Dispers 688, Tego®Dispers 690, Tego®Dispers 710 by Evonik.
- the ink according to the disclosure may contain (by weight relative to the total weight of the ink) between 2 and 20% of the dispersing agent, advantageously between 5 and 15%.
- the ink according to the present disclosure does not contain any bentonite clay.
- the present disclosure also concerns the process of preparation of the non-aqueous gel writing ink according to the present disclosure.
- the fatty acid amide wax is activated by formation of a premix in a solvent, advantageously the solvent as described above for the ink, in particular glycol ether, more advantageously phenoxyethanol, before its addition in the writing ink containing the solvent and the coloring agent, the silica particles and optionally the additive.
- a solvent advantageously the solvent as described above for the ink, in particular glycol ether, more advantageously phenoxyethanol, before its addition in the writing ink containing the solvent and the coloring agent, the silica particles and optionally the additive.
- the activation step (formation of a premix) is carried out at a precise temperature and shear stress. Therefore advantageously, the activation step (formation of a premix) is carried out at a temperature of between 30 and 70° C., more advantageously between 40 and 60° C., still more advantageously at 60° C., with a shear rate of between 20 and 25 m/s.
- a rotor-stator disperser can be used.
- the perfect activation is physically visible by measuring viscosity at rest of the premix. When activation is complete, viscosity at rest is maximal (spreading polyamide wax chains increases the rest viscosity, destroying the chains decreases the rest viscosity).
- the viscosity measured at 20° C. with a cone-and-plate rheometer such as the Malvern KINEXUS rheometer with a cone of 40 mm and an angle of 4°, of the premix obtained is more than two million mPa ⁇ s at a shear rate of 0.01 s ⁇ 1 ; the premix obtained is between 500 and 1500 mPa ⁇ s at a shear rate of 100 s ⁇ 1 preferably between 800 and 1300 mPa ⁇ s at a shear rate of 100 s ⁇ 1 ; the premix obtained is between 100 and 400 mPa ⁇ s at a shear rate of 1000 s ⁇ 1 , preferably between 200 and 350 mPa ⁇ s at a shear rate of 1000 s ⁇ 1 .
- the addition of the fatty acid amide wax, in particular in the form of a premix, to the writing ink already containing the solvent, the silica particles and the coloring agent, in particular the dyes, is carried out at a precise temperature, advantageously of between 50 and 60° C. Indeed, with the same amount of premix, higher loading temperature brings to higher rest viscosity and higher stable rest viscosity after three months of storage. This is due to a second activation of the fatty acid amide wax with the dyes.
- This temperature has also an inverse impact on the viscosity return after writing. The lower the temperature, the quicker is the return to rest viscosity after writing. If the return to rest temperature is too long, static leakage can occur in the few minutes after writing and in case the coloring agent is a pigment, pigments settlement could start. It is preferable for the static leakage to be ⁇ 1.0 mm.
- the present disclosure also concerns the use of a mixture of silica particles and of a fatty acid amide wax as a gelling agent in a non-aqueous gel writing ink.
- the present disclosure concerns a writing instrument, in particular a pen such as a ball-pen, containing the ink according to the present disclosure.
- the viscosity is measured at 20° C. using a cone-and-plate rheometer Malvern KINEXUS with a cone of 40 mm and an angle of 4°.
- Table 1 below contains the composition of an ink according to the present disclosure.
- the ink has been prepared by first activating the fatty acid amide wax (CRAYVALLAC SUPER®) by preparing a premix as follow:
- This process allows the activation of CRAYVALLAC SUPER® in order for it to adequately play its gelling agent function.
- the premix has the following viscosity at 20° C.:
- the dispersion time is 50 minutes by using a stator/rotor disperser with a shear rate of between 20 and 25 m/s.
- Contacting the premix with the ink formulation is carried out at a temperature of between 50 and 60° C. in order to obtain the best compromise between the immediate return to the rest viscosity after writing and storage for three months at 40° C. and 80% relative humidity.
- EXAMPLE 2 COMPARISON BETWEEN THE GELLING AGENT ACCORDING TO THE DISCLOSURE AND OTHER GELLING AGENTS
- CRAYVALLAC SUPER® containing octadecanamide (the fatty acid amide wax according to the present disclosure) which has been activated by preparing a premix as indicated in example 1;
- Thixatrol MAX® from Elementis which is a mixture of N,N′-ethane-1,2-diylbis(hexanamide) (or N,N′-Ethylenebis(capronamide)), 12-hydroxy-N-[2-[(1-oxyhexyl)amino]ethyl]octadecanamide and N,N′-ethane-1,2-diylbis(12-hydroxy octadecanamide) having the respective following formula: CH 3 (CH 2 ) 4 CONH(CH 2 ) 2 NHCO(CH 2 ) 4 CH 3 CH 3 (CH 2 ) 4 CONH(CH 2 ) 2 NHCO(CH 2 ) 10 CHOH(CH 2 ) 5 CH 3 and CH 3 (CH 2 ) 5 CHOH(CH 2 ) 10 CONH(CH 2 ) 2 NHCO(CH 2 ) 10 CHOH(CH 2 ) 5 CH 3 ) (another fatty acid amide wax according to the disclosure).
- CRAYVALLAC MT® from ARKEMA which is a castor oil modified polyamide (comparative gelling agent). It has been activated by preparing a premix as follow: addition of 2.8% by weight of CRAYVALLAC MT® in phenoxypropanol at a temperature of 60° C. by using a stator/rotor disperser with a shear rate of between 20 and 25 m/s.
- the initial viscosity at rest (0.01 s ⁇ 1 /20° C.), the shear viscosity at 100 s ⁇ 1 and the immediate rest return (0.01 s ⁇ 1 ) at 20° C. of the ink composition according to example 1 have been compared with the viscosity of the same ink composition in which the gelling agent (mixture of fatty acid amide wax+silica particles) has been replaced by 0.7% by weight of silica particle (Aerosil® 200) (comparative example 1) or by 0.4% by weight of silica particle (Aerosil® 200)+0.3% by weight of bentonite clay (Bentone SD-2) (comparative example 2).
- the gelling agent mixture of fatty acid amide wax+silica particles
- silica particles are added in the form of a 10% premix in phenoxyethanol at 20° C. in the ink composition containing the other ingredients and the rest of the silica particles.
- the static leakage of the ink according to example 1 has been compared with an ink composition with the static leakage of the same ink composition in which fatty acid amide wax is used as the only gelling agent (no silica particles are present in the ink composition) (Comparative example 3) or in which the fatty acid amide wax is used in combination with 0.4% by weight of bentonite clay (Bentone SD-2) (Comparative example 4).
- the experimental protocol is as follow:
- the static leakage is measured by taking the drop formed at the tip of the pen on a paper sheet.
- the drop is then covered by a transparent adhesive tape and then circularly spread with a wallpaper roller.
- the obtained stain diameter is then measured.
- the static leakage at 40° C./80% corresponds to the spread diameter of the drop formed after storage of the pen with the tip down during a week in a climatic chamber at 40° C. and 80% relative humidity.
- the static leakage at 23° C./50% corresponds to the spread diameter of the drop formed after storage of the pen with the tip down during 24 hours in a climatic chamber at 23° C. and 50% relative humidity.
- EXAMPLE 3 COMPARISON BETWEEN THE DIFFERENT TEMPERATURES OF ADDITION OF THE PREMIX OF THE FATTY ACID AMIDE WAX ACCORDING TO THE DISCLOSURE IN THE INK COMPOSITION ACCORDING TO EXAMPLE 1
- a premix of the fatty acid amide wax has been prepared as follow:
- This process allows the activation of the fatty acid amide wax in order for it to adequately play its gelling agent function.
- the premix has the following viscosity at 20° C.:
- the quantity of premix added to the ink composition according to example 1 depends on the temperature at which it is added to the ink.
- the best compromise is therefore using a temperature of between 50° C. and 60° C. for the addition of the premix in the ink composition according to the present disclosure.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Pens And Brushes (AREA)
Abstract
Description
12-hydroxy-N-[2-[(1-oxyhexyl)amino]ethyl]octadecanamide of the following formula CH3(CH2)4CONH(CH2)2NHCO(CH2)10CHOH(CH2)5CH3, N,N′-ethane-1,2-diylbis(12-hydroxy octadecanamide) of the following formula CH3(CH2)5CHOH(CH2)10CONH(CH2)2NHCO(CH2)10CHOH(CH2)5CH3) and mixture thereof.
12-hydroxy-N-[2-[(1-oxyhexyl)amino]ethyl]octadecanamide of the following formula CH3(CH2)4CONH(CH2)2NHCO(CH2)10CHOH(CH2)5CH3, N,N′-ethane-1,2-diylbis(12-hydroxy octadecanamide) of the following formula CH3(CH2)5CHOH(CH2)10CONH(CH2)2NHCO(CH2)10CHOH(CH2)5CH3) and mixture thereof.
N,N′-Ethylene-bis-12-hydroxystearamide of the following formula CH3(CH2)5CHOH(CH2)10CONH(CH2)2NHCO(CH2)10CHOH(CH2)5CH3, N,N′-Ethylenebis(caprinamide) of the following formula CH3(CH2)8CONH(CH2)2NHCO(CH2)8CH3 and mixture thereof.
In a particular embodiment, the fatty acid amide wax comprises octadecanamide of the following formula
More particularly, the fatty acid amide wax is a mixture of the three following fatty acid amide waxes:
TABLE 1 | |||
Content | |||
Trade name | Chemical name | Function | in wt. % |
Phenoxyethanol(EPH) | Phenoxyethanol | solvent | 52.3 |
Aerosil 200 ® | Fumed silica | GELING agent | 0.4 |
Solvent Black 46 ® | Solvent black 46 | dye | 25 |
Lonzest SOC ® | Sorbitan | Clear drain | 1.3 |
Sesquioleate | agent | ||
Ketonic Resin | Resin | Viscosity agent | 13.5 |
CRAYVALLAC | fatty acid amide | GELING | 7.5 |
SUPER ® | wax at 5% in | AGENT | |
phenoxyethanol | |||
Total | 100 | ||
The viscosity of the ink is as follow:
TABLE 2 | ||
Rest viscosity (0.01 s−1/20° C.) |
Ink color | Black | Blue | Red | Green | Pink |
Mix of dyes | Triarylmethane + | Triarylmethane + | Xanthene + | Phtalocyanine + | Xanthene |
Azoic | Phtalocyanine | Azoic | Azoic | ||
Viscosity of | 2500 mPa · s | 2200 mPa · s | 6270 mPa · s | 4200 mPa · s | 1200 mPa · s |
solvent + dyes | |||||
solution | |||||
Increase of | + | − | + | − | +++ |
rest viscosity | |||||
with 0.5% | |||||
CRAYVALLAC | |||||
MT ® | |||||
Increase of | ++ | ++ | ++ | + | +++ |
rest viscosity | |||||
with 0.5% | |||||
THIXATROL | |||||
MAX ® | |||||
Increase of | +++ | +++ | +++ | +++ | +++ |
rest viscosity | |||||
with 0.5% | |||||
CRAYVALLAC | |||||
SUPER ® | |||||
−: no viscosity change | |||||
+: +1000 to + 5000% rest viscosity | |||||
++: +5000 to + 10 000% rest viscosity | |||||
+++: >+10 000% rest viscosity | |||||
Crayvallac MT ® allows creating a good network only with pink ink and creates a poor network with black & red inks and no network at all with blue and green inks. |
Therefore it cannot be used as a gelling agent according to the present disclosure.
Thixatrol MAX® and Crayvallac Super® provide a good gelling network, the strength of the gelling network being better with Crayvallac Super®, whatever the type of dye used.
TABLE 3 | |||
Initial rest | |||
viscosity | Shear viscosity | Immediate rest return | |
type of gelling | (0.01 s−1) | (100 s−1) | (0.01 s−1) |
agent | at 20° C. | at 20° C. | at 20° C. |
Example 1 | 53 000 | 2100 | 8000 |
Comparative | 2600 | 2300 | 2330 |
Example 1 | |||
Comparative | 2270 | 2100 | 2020 |
Example 2 | |||
As can be seen in this table, silica alone and a mixture of silica and clay do not impart a sufficient viscosity at rest to the ink composition in order to form a gel writing ink.
TABLE 4 | ||
Static leakage at | Static leakage at | |
type of gelling agent | 40° C./80% | 23° C./50% |
Example 1 | 1.0 mm | 1.1 mm |
Comparative Example 3 | 10.5 mm | 3.5 mm |
Comparative Example 3 | 3.9 mm | 3.3 mm |
TABLE 5 | |||
Temperature of | Quantity of premix needed | ||
addition of | to reach viscosity of | ||
the premix | 50 000 mPa · s at rest | ||
in the ink | (0.01 s−1) at 20° C. | ||
30° C. | 15% | ||
40° C. | 7% | ||
50° C. | 6% | ||
60° C. | 4% | ||
TABLE 6 | |||
Rest viscosity | Rest viscosity | ||
after 1 month | after 1 month |
Premix | Initial rest | Shear | Immediate | storage at | storage at |
addition | viscosity | viscosity | rest return | 20° C. and 50% | 40° C. and 80% |
temperature | (0.01 s−1) | (100 s−1) | (0.01 s−1) | RH (Temperate | RH (Tropical |
(° C.) | at 20° C. | at 20° C. | at 20° C. | climate) | climate) |
30° C. | 50 000 | 2500 | 65 000 | mPa · s | 108 000 | mPa · s | 106 000 | mPa · s |
40° C. | mPa · s | mPa · s | 10 000 | mPa · s | 50 000 | mPa · s | 70 000 | mPa · s |
50° C. | 8 000 | mPa · s | 50 000 | mPa · s | 30 000 | mPa · s | ||
60° C. | 8000 | mPa · s | 40 000 | mPa · s | 25 000 | mPa · s | ||
Claims (17)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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EP17306876.8 | 2017-12-21 | ||
EP17306876.8A EP3502197A1 (en) | 2017-12-21 | 2017-12-21 | Writing gel ink |
EP17306876 | 2017-12-21 | ||
PCT/EP2018/085993 WO2019122017A1 (en) | 2017-12-21 | 2018-12-19 | Writing gel ink |
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US11891530B2 true US11891530B2 (en) | 2024-02-06 |
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US (1) | US11891530B2 (en) |
EP (2) | EP3502197A1 (en) |
JP (1) | JP7401431B2 (en) |
CN (1) | CN111344365A (en) |
AR (1) | AR113661A1 (en) |
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EP4021989B1 (en) * | 2019-08-29 | 2023-08-09 | Société BIC | Process of preparation of an aqueous gel ink with variable color comprising silver nanoparticles |
EP3872141A1 (en) * | 2020-02-28 | 2021-09-01 | Société BIC | Writing gel ink for pens without follower |
EP3872142A1 (en) * | 2020-02-28 | 2021-09-01 | Société BIC | Writing gel ink |
EP3943560A1 (en) | 2020-07-24 | 2022-01-26 | Société BIC | Writing gel ink |
WO2021170822A1 (en) * | 2020-02-28 | 2021-09-02 | SOCIéTé BIC | Writing gel ink |
WO2024085034A1 (en) * | 2022-10-20 | 2024-04-25 | 株式会社パイロットコーポレーション | Ink composition for oil-based ballpoint pen and oil-based ballpoint pen using same |
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2017
- 2017-12-21 EP EP17306876.8A patent/EP3502197A1/en not_active Withdrawn
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2018
- 2018-12-19 US US16/956,038 patent/US11891530B2/en active Active
- 2018-12-19 CN CN201880073759.9A patent/CN111344365A/en active Pending
- 2018-12-19 EP EP18826641.5A patent/EP3697857B1/en active Active
- 2018-12-19 BR BR112020010217-2A patent/BR112020010217A2/en active IP Right Grant
- 2018-12-19 WO PCT/EP2018/085993 patent/WO2019122017A1/en unknown
- 2018-12-19 JP JP2020528456A patent/JP7401431B2/en active Active
- 2018-12-19 MX MX2020005274A patent/MX2020005274A/en unknown
- 2018-12-20 AR ARP180103743A patent/AR113661A1/en active IP Right Grant
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BR112020010217A2 (en) | 2020-11-10 |
MX2020005274A (en) | 2020-08-17 |
US20210108099A1 (en) | 2021-04-15 |
WO2019122017A1 (en) | 2019-06-27 |
EP3502197A1 (en) | 2019-06-26 |
EP3697857B1 (en) | 2021-04-21 |
CN111344365A (en) | 2020-06-26 |
AR113661A1 (en) | 2020-05-27 |
JP2021507950A (en) | 2021-02-25 |
JP7401431B2 (en) | 2023-12-19 |
EP3697857A1 (en) | 2020-08-26 |
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